Citric acid, an important metabolite with abundant reactive groups, has been demonstrated as a promising starting material to synthesize diverse photoluminescent materials including small molecules, polymers, and carbon dots. The unique citrate chemistry enables the development of a series of citric acid-based molecules and nanomaterials with intriguing intrinsic band-shifting behavior, where the emission wavelength shifts as the excitation wavelength increases, ideal for chromatic imaging and many other applications. In this review, we discuss the concept of “intrinsic band-shifting photoluminescent materials”, introduce the recent advances in citric acid-based intrinsic band-shifting materials, and discuss their potential applications such as chromatic imaging and multimodal sensing. It is our hope that the insightful and forward-thinking discussion in this review will spur the innovation and applications of the unique band-shifting photoluminescent materials.